Organic peroxides derived from unsaturated compounds

ABSTRACT

New organic peroxides having the formula   may be prepared by reacting a monohydroperoxide selected from R5OOH and R6OOH with an unsaturated carbonyl compound having the formula   the reaction being carried out in the presence of an acid catalyst at a temperature between about -30*C and +80*C, the molar ratio of the carbonyl compound to the hydroperoxide being between about 1:2 and 1:10. The new organic peroxides are particularly useful for crosslinking plastomers, vulcanizing elastomers, and as initiators for radical polymerizations.

United States Patent [191 Sacrini et al.

[ ORGANIC PEROXIDES DERIVED FROM UNSATURATED COMPOUNDS [75] Inventors: Egeo Sacrini; Claudio Cavallotti,

both of Milan, Italy [73] Assignee: The B. F. Goodrich Company, Akron, Ohio 22 Filed: Mar. 3, 1975 21 Appl. No.: 554,474

Related US. Application Data [62] Division of Ser. No. 53,267, July 8, 1970.

[30] Foreign Application Priority Data July 29, 1969 Italy 20222/69 [52] US. Cl 260/610 R [51] Int. Cl. C07C 179/00; C07C 179/06 [58] Field of Search 260/610 R [56] References Cited UNITED STATES PATENTS 3,296,184 l/l967 Portolani et al. 260/610 R Primary Examiner-James 0. Thomas, Jr. Assistant ExaminerW. B. Lone Attorney, Agent, or Firm-Hubbell, Cohen, & Stiefel 1 3,928,466 Dec. 23, 1975 [57] ABSTRACT New organic peroxides having the formula the reaction being carried out in the presence of an acid catalyst at a temperature between about 30C and +80C, the molar ratio of the carbonyl compound to the hydroperoxide being between about 1:2 and 1:10. The new organic peroxides are particularly useful for crosslinking plastomers, vulcanizing elastomers, and as initiators for radical polymerizations.

7 Claims, No Drawings ORGANIC PEROXIDES DERIVED FROM UNSATURATED COMPOUNDS This is a division of application Ser. No. 53,267, filed July 8, 1970.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to new organic peroxides and more particularly to new organic peroxides which have a double peroxidic function and are derived from unsaturated compounds, as well as to the use of these new organic peroxides in the crosslinking of plastomers, in the vulcanization of elastomers and as organic reactants.

2. Description of the Prior Art Organic peroxides are used as initiatorsfor radical polymerization, vulcanizing agents for elastomers, and cross-linking agents for thermoplastic polymers. A discussion of typical organic peroxides used in the prior art, their preparation, and some difficulties associated with the preparation and use of some prior art peroxides appears in U.S. Pat. No. 3,489,730, which was issued Jan. 13, 1970, to the assignee hereof and the contents of which are hereby incorporated herein by reference.

The present invention provides a particular class of new organic peroxides having good stability and low volatility, which peroxides are particularly suited and interesting both as cross-linking agents for plastomers and as vulcanizing agents for elastomers.

SUMMARY OF THE INVENTION The present invention provides a new series of peroxides with a double peroxidic function characterized by one or more unsaturated bonds and having the general formula:

OOR,

wherein R is selected from the group consisting of unsubstituted, alkyl substituted and halogen substituted cycloalkyl radicals having 5-30 C; unsubstituted, alkyl substituted, hydroxy substituted and halogen substituted phenyl radicals having 6-26 C: and unsubstituted, alkyl substituted and halogen substituted heterocyclic radicals having 4-15 C; R is selected from the group consisting of hydrogen, alkyl radicals having l-12 C, unsubstituted, alkyl substituted and halogen substituted cycloalkyl radicals having 5-20 C halogen substituted alkyl radicals having l-l2 C; and unsubstituted, alkyl substituted and halogen substituted phenyl radicals;

and R and R together with the carbon atom towhich they are bonded may form a cycloaliphatic ring selected from the group consisting of unsubstituted and alkyl, phenyl, phenylalkyl, alkylidene and phenylalkylidene substituted cycloaliphatic rings having 5-30 C; R and R are each selected from the group consisting of hydrogen, alkyl radicals having 1-12 C, unsubstituted,

alkyl substituted and halogen substituted cycloalkyl,

C; and R and R taken together with the two adjacent carbon atoms to which they are respectively bonded may form a cycloaliphatic ring selected from the group consisting of unsubstituted and alkyl, phenyl, phenylalkyl, alkylidene, phenylalkylidene and hydroxy phenylalkylidene substituted cycloaliphatic rings having 5-25 C; R and R are each selected from the group consisting of alkyl radicals having 4-12 C, phenylalkyl radicals having 9-18 C, unsubstituted, alkyl substituted and halogen substitutedcycloalkyl radicals having 5-21 C; unsubstituted, alkyl substituted and halogen substituted phenylcycloalkyl radicals having 9-25 ,C; halogen substituted alkyl radicals having 4-12 C, and halogen substituted phenylalkyl radicals having 9-18 C.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Tertiary alkyl groups, for example, ter.-butyl, ter.- amyl and cumyl, are preferred as the R and R radicals. I

Examples of compounds of the present invention, within the above general formula, include:

q) l-phenyl-3,3-di(cyclohexen-2-yll -ethyl-peroxy)- propene-l; K

r) l-phenyl-3,3-di(tetralin l-peroxy)propene-l;

s) 1-phenyl-3 ,3-di( tetralin-l -methyl-l -peroxy)propene-l The diperoxides of this invention have the unusual properties of havinggood stability and low volatility at temperatures higher than room temperature. These properties permit the compounds to be incorporated in plastomers as crosslinking agents and in saturated elastomers as vulcanizingagents without giving rise to the troublesome secondary phenomena (for instance prevulcanization and pre-crosslinking) which arise when using less stable, more volatile, prior art peroxides,

In ac :cordance w ithv a preferred embodiment, the diperoxides of the invention maybe prepared by facting an unsaturated carbonyl derivative, dissolved in a suitable solvent, with an arganie hydlperoxid in the presence of an acid catalyst at a temperature between about -3 0 and +s0c,. ref rably between about -10 and +50C. y

Theunsaturated carbonyl corfiQQllhdE whieh maybe used in the foregoing reaction have the general formula f aft wherein R R R and R are as defined above. Examples of such carbonyl compounds include, for instance, cinnamic aldehyde, furyl-acrylic aldehyde, alphacyclo-hexylidene-acetaldehyde, alpha-benzylideneacetone and 2,6-benz'ylidene-cyclohexanone.

The hydroperoxides which may be used in the reaction have the general formula ROOH wherein R represents R and R as defined above. Examplesof such compounds include: ter.-butyl hydroperoxide, ancl substituted derivatives thereof; cumyl-hydroperoxide and substituted derivatives thereof; 1,3-diisopropylbenzene-a-monohydroperoxide and 1,4 diiso-propylbenzene-a-monohydroperoxide; l-methyl-cyclohexylhydroperoxide; 2-methyl-2-hydroperoxy-butyn-3; 1- menthane-hydroperoxide; and l-phenyl-cyclohexyl hydroperoxide.

The solvents which may be employed in the reaction include for example, linear aliphatic hydrocarbons having 6 to C, linear aliphatic halogenated hydrocarbons having 1 or 2 C andfrom l to 4 Cl aromatic hydrocarbons, having from 6 to 9 C, which may be halogenated with l or 2 Cl, cycloaliphatic hydrocarbons having 6 to 10 C, and ethers, for instance ethylether.

The molar ratio of unsaturated carbonyl compound to hydroperoxide is between about 1:2 and 1:10, preferably between about 122.5 and 1:5.

The catalysts used are preferably sulfonic acids, such as for instance, para-toluene sulphoriic acid.

The new diperoxides of the present invention are soluble in chlorinated and unchlorinated aliphatic and aromatic hydrocarbon solvents, and in aliphatic esters. A particular feature of this invention is that the diperoxides of this invention are excellent crosslinking agents for plastomers, vulcanizing agents for elastomers and initiators for radical polymerization. The use of the diperoxides defined above for the crosslinking of plastomers is particularly applicable to the polyolefins and more particularly to polyethylene.

The crosslinking of polyethylene with the peroxides of the present invention results in a product having improved mechanical properties at high temperatures, reduced fragility at low temperatures and reduced solubility in aliphatic and aromatic hydrocarbons, even chlorinated ones. Furthermore, the crosslinked polyethylene has increased resistance tolight, weather and to ageing.

The crosslinking is carried out in accordance with this aspect of the present invention at a temperature between about 100 and 200C, preferably between about 145 and 165C, at a pressure between about 50 and 200 kg/cm and for periods of from about 5 to 60 minutes, preferably from about 10 to 30 minutes. The concentration of the peroxide is between about 0.5 and 10 percent by weight, preferably between about 2 and 5 percent by weight, based on the weight of the plastomer.

The vulcanization of elastomers, for example, ethylene/propylene copolymers, in accordance with the present invention may be carried out at a temperature between about 140 and 190C. preferably between about 150 and 170C, for periods of from about 5 to 200 minutes, preferably between about 5 to 15 4 minutes. The concentration of the peroxide is between about 0.5 and 10 percent by weight, preferably between about 2 and 5 percent by weight, based on the weight of the elastomer.

Particularly suitable vulcanization mixes for vulcanizing ethylene/propylene copolymer have compositions within the following ranges:

ethylene/propylene 100 parts by weight copolymer I carbon black 20 to parts by weight ZnO l to 10 parts by weight sulfur 0.15 to 0.5 parts by weight peroxide 0.005 to 0.02 moles.

The most notable advantages afforded by the use of the diperoxides of the present invention in the crosslinking of plastomers and in the vulcanization of saturated elastomers include: partically odorless crosslinked and vulcanized products; absence of blooming phenomena; short vulcanization times and low vulcanization temperatures; the greater effectiveness of the new diperoxides remains unaltered even in the presence of known fillers, reinforcing agents (for instance carbon black, Mg hydrosilicate), additives of the type ageing resistant plastified and homogenized masses can be obtained without pre-crosslinking or pre-vulcanization phenomena which hinder the further processing.

The possibility of obtaining plastified and homogenized masses without pre-crosslinking or pre-vulcanization phenomena is due to the fact that the peroxides do not thermally decompose to the mixing temperature giving rise to the beginning of the pre-crosslinking and pre-vulcanization phenomena.

The following examples are presented to further illustrate the present invention.

EXAMPLE 1 200 g of anhydrous benzene and 131.5 g of 80% ter-butyl hydroperoxide were introduced into a flask at ambient temperature provided with a stirrer. The temperature was then increased to 40C and, during 10 minutes, there were simultaneously added 51.6 g of 98% cinnamic aldehyde and 100 g of a benzene/methanol solution of paratoluensulfonic acid, having the following composition by weight:

0.14% of paratoluenesulfonic acid, 1.42% of anhydrous methanol, and 98.44% of anhydrous benzene.

-The mixture was then stirred for 3 hours at 40C. Thereafter, the organic solution was washed with 8% aqueous solution of NaHCO then with 5% aqueous NaOH, and finally with water to a pH of 6.5.

The solvent was then removed under vacuum (final pressure, 0.2 mm Hg) at 30C, obtaining 92 g ofa white crystalline product as residue.

After repeated recrystallizations from methanol, there were obtained 75 g of a solid crystalline product which was identified as l-phenyl-3,3-di(ter.-butylperoxy)-pro'pene-l. This product had product had the following characteristics:

melting point: 98-99C iodometric titer: 98% decompositiontemperature: l 18C half life at C: 30 minutes carbon content, weight found: 69.0 carbon content, weight calculated: 69.36

-continued hydrogen content, weight found: 9. hydrogen content, weight calculated: 8

EXAMPLE 2 200 g of normal hexane and 120 g of 90% ter.-butyl hydroperoxide were introduced into a flask at ambient temperature provided with a stirrer. The temperature 7 was increased to 42 to 45C and, during 10 minutes, there were simultaneously introduced 48.8 g of distilled furyl-acrvlic aldehyde and 160 g of a benzene/methanol solution of paratoluenesulfonic acid having the following composition by weight:

1.42% of anhydrous methanol, 98.44% of anhydrous benzene and 0.14% of paratoluenesulfonic acid, i.e., the same composition as the solution employed in Example 1.

This mixture was then stirred for 3 hours and 30 minutes at a temperature of 42 to 45C. The organic solution was then washed with water, with an 8% Nal-l- CO solution and then again with water to a pH of 6.5. The solvent was removed under vacuum at 40C, with v a final pressure of 0.2 mmHg.

The solid residue 1 19 g) was crystallized from methanol and there were thus obtained 101 g of a light yellow crystalline product which was identified as 1- furyl-3 ,3-di(ter.-butylperoxy)-propene-1.

The product had the following characteristics:

iodometric titration: 77.6% n 1.5586 decomposition temperature: 125C half life at 119C: 1 30 minutes carbon content, weight found: 77.0% carbon content, weight calculated: 77.4% hydrogen content, weight found: 7.3% hydrogen content, weight calculated: 7.22%.

EXAMPLE 4 vulcanization The vulcanization tests were carried out on mixes of an ethylene/propylene copolymer, having a molar ratio ethylene/propylene 50/50 and a viscosity Mooney ML( 1+4) 100C 35. In Table 1 there are compared the vulcanization rates determined on equivalent mixes containing as peroxides, respectively, 1-phenyl-3,3-di(- ter.-butyl-peroxy)-propene-1; 1-furyl-3,3-di(ter.-butylperoxy)-propene-1 and dicumyl peroxide.

The vulcanization rate was determined at 177C on a Monsanto TM-10 rheometer. The mixes used had the melting point: 56-S7C iodometric titer: 99.5% follQwmg p decomposition temperature: 104C half life at 1 18C: 30 minutes i carbon content, weight found: 64.0% elhylerw/pmpylene copolymer 100 Parts y weyght carbon content, weight calculated: 63.36% carbon black P y s hydrogen content, weight found: 8.7% Zno 3 1 y as hydrogen content, weight calculated: 8.51%. z lgi 1:3 :1 welght TABLE 1 vulcanization rate Parts per 100 g of ethyvulcanization vulcanization Peroxide lene/propylene copol mer temperature time g mo es C minutes -c|-l=cH-c 2.94 0.01 177 6 lCRm :t)a UCH=CHC 2.84 0.01 177 5 Dicumylperoxide 0.01 177 14 EXAMPLE 3 Table 2 compares the physical properties of the vulcanized products obtained by the use of 1-phenyl-3,3- di(ter.-butyl-peroxy)-propene- 1; and 1-furyl-3 ,3-di(- ter.-butyl-peroxy)-propene-1, at vulcanization times between 5 and 60 minutes, at a vulcanization temperature of C, with those of the vulcanized products obtained using dicumyl peroxide at C for 30 minutes (these being the .optimal conditions for dicumyl peroxide).

From the results set forth in Table 2 it appears evident that the peroxides of the present invention permit the use of a low vulcanization temperature while affording high vulcanization rates and better physical ylene in a test tube containing 100 cc of xylene stabilized with 0.1 g of phenolic antioxidant, i.e., 4,4-thiobis(3-methy1-6-ter.-butyl-phenol). The operation is carried out at 80C for 21 hours. The degree of swelling characteristics of the vulcanized product than those 5 is given by the following formula: obtained by using dicumylperoxide at higher temperal 07 I (a b) c I ture (165C) for longer periods of time (30 minutes).

TABLE 2 vulcanization Physical Properties of the Vulcanized Products Parts per 100 parts Tensile Elonga- Modulus Modulus Modulus of ethylene/ Temp Time strength tion at at 100% at 200% at 300% Peroxide prop lene erabreak Elonga- Elonga- Elonga- RHD copo ymer ture minkg/cm tion tron t|on hard- C utes ness moles g. kg/cm kg/cm lag/cm OOC(CH 0.015 4.41 150 215 550 20 43 92 63 CH=CHCH 10 218 460 25 66 127 65 OCC(C 192 370 24 67 137 65 30 208 400 25 71 138 65 60 192 400 25 65 133 65-66 OOC(CH;,) 0.010 3.41 150 5 134 I 350 26 60 106 66 CH=CHCH\ 10 145 390 27 60 104 66 o OOC(C 15 149. 400 25 57 102 66 125 320 25 59 106 66 60 136 360 25 62 109 65 Dicumylperoxide 0.010 2.70 165 30 180 410 21 58 119 68 EXAMPLE 5 wherein a weight of the test sample after 21 hours at Crosslinking C in xylene, b weight of test sample before the The crosslinking tests were carried out on mixes of low-density (0.918) polyethylene and peroxide. Table 3 sets forth the physical properties of the polyethylene crosslinked by using, respectively, the diperoxides prepared in Example 1 (1-phenyl-3,3-di(ter.-butyl-peroxy)-propene-l Example 2 (1-furyl-3,3-di(ter.-butylperoxy)-propene-l), and a known diperoxide (dicumylperoxide).

The results thus obtained show the excellent crosslinking activity of the diperoxides of the invention.

test, c weight of test sample after drying at the end of the test,

density of polyethylene at 80C 2 density of xylene at 80 C TABLE 3 Moles of Crosslinking Physical Characteristics peroxide Temp- Yield Tensile Elonga- Degree of swell- Peroxlde m g Time erapoint strength tion at ing in x 101 at of mmutes ture break 80C for 1 hours polyethylene C kg/cm kg/cm in None 20 145 57.8 73 150 soluble OC(CH C H,,CH=CHCH 0.01 20 145 52 150 240 10.4

OOC(CH l mm) CH=CH-C 0.01 20 145 57 400 14 o OOC(CH Dicumylperoxide 0.01 20 52.9 132 456 21.3

The test method consists of suspending a small basket containing a plate of about 0.2 g of crosslinked polyethto secure by Letters Patent and hereby claim is: 1. An organic peroxide having the formula:

' QOR wherein R is selected from the group consisting of alkyl and cycloalkyl radicals having -30 carbon atoms; and alkyl and hydroxy substituted phenyl radicals having 6-26 carbon atoms; R is selected from the group consisting of hydrogen, alkyl and cycloalkyl radicals having 52() carbon atoms; alkyl radicals having 1-12 carbon atoms, and alkyl substituted phenyl radicals; and R and R together with the carbon atom to which they are bonded may form a cycloaliphatic ring selected from the group consisting of alkyl, phenyl, phenylalkyl, alkylidene and phenylalkylidene substituted cycloaliphatic rings having 5-30 carbon atoms; R and R are each selected from the group consisting of hydrogen, alkyl and cycloalkyl radicals having 5-20 carbon atoms; alkyl substituted phenyl radicals having 6-20 carbon atoms; alkyl radicals having 1-12 carbon atoms, and phenylalkyl radicals having 7-20 carbon atoms and R and R taken together with the two adjacent carbon atoms to which they are respectively bonded may form a cycloaliphatic ring selected from the group consisting of alkyl. phenyl, phenylalkyl, alkylidene, phenylalkylidene and hydroxyphenylalkylidene substituted cycloaliphatic rings having 5-25 carbon atoms; R and R are each selected from the group consisting of alkyl cycloalkyl radicals having 5-21 carbon atoms; alkyl substituted phenylcycloalkyl radicals having 9-25 carbon atoms; alkyl radicals having 4-12 carbon atoms, and phenylalkyl radicals having 9-18.

carbon atoms.

2. The peroxide of claim 1 which is selected from the group consisting of l-phenyl-3 ,3-di(ter.-butyl-peroxy )-propene-l;

- l-phenyl-3,3-di(cumyl-peroxy)-propene-l;

l-phenyl-3,3-di(ter.-butyl-peroxy)-butene-l; l-phenyl-3,3-di(cumyl-peroxy)-butene-1; 1-phenyl-3-ter.-butyl-peroxy-3-cumyl-peroxybutene-l; l-cyclohexylidene-2,2-di(ter.-buty1-peroxy)-ethane; l ,1-di(ter.-butyl-peroxy)-2-benzylidene-cyclohexane; 1,1 -di(ter.-butyl-peroxy )-2,6-di(4-hydroxy-benzylidene)cyclohexane; 1 l -di(ter.-butyl-peroxy)-2,6-di(4-isopropyl-benzylidene)cyclohexane; l-cyclohexyl-3,3-di(ter.-butyl-peroxy)-butene-l; 2,3-di(phenyl)-4-di(ter.-butyl-peroxy)-butene-2; 1-phenyl-3 ,3-di(cyclohexen-2-yll -peroxy)propene- 1-phenyl-3 ,3-di(cyclohexen-2-yl-l-ethyl-1-peroxy)- propene-l;

1-phenyl-3 ,3-di(tetralinl -peroxy)propene-1 and l-phenyl-3 ,3-di(tetralin-l -methyl-l -peroxy)propene-l 3. A process for the preparation of an organic peroxide having the formula:

OOR

wherein R is selected from the group consisting of alkyl and cycloalkyl radicals having 5-30 carbon atoms; and alkyl and hydroxy substituted phenyl radicals having 6-26 carbon atoms; R is selected from the group consisting of hydrogen, alkyl and cycloalkyl radicals having 5-20 carbon atoms, alkyl radicals having 1-12 carbon atoms and alkyl substituted phenyl radicals; and R and R together with the carbon atom to which they are bonded may form a cycloaliphatic ring selected from the group consisting of alkyl, phenyl, phenylalkyl, alkylidene and phenylalkylidene substituted cycloaliphatic rings having 5-30 carbon atoms; R and R are each selected from the group consisting of hydrogen, alkyl and cycloalkyl radicals having 5-20 carbon atoms; alkyl substituted phenyl radicals having 6-20 carbon atoms; alkyl radicals having 1-12 carbon atoms, and phenylalkyl radicals having 7-20 carbon atoms; and R and R taken together with the two adjacent carbon atoms to which they are respectively bonded may form a cycloaliphatic ring selected from the group consisting of alkyl, phenyl, phenylalkyl, alkylidene, phenylalkylidene and hydroxyphenylalkylidene substituted cycloaliphatic rings having 5-25 carbon atoms; R and R are each selected from the group consisting of alkyl and cycloalkyl radicals having 5-21 carbon atoms; alkyl and phenylcycloalkyl radicals having 9-25 carbon atoms; alkyl radicals having 4-12 carbon atoms and phenylalkyl radicals having 9-18 carbon atoms, this process comprising reacting a hydroperoxide selected from the group consisting of R OOl-l and R OOl-l, wherein R and R are as defined above, with an unsaturated carbonyl compound, having the formula:

wherein R R R R are as defined above dissolved in a suitable solvent in the presence of a sulfonic acid catalyst at a temperature between about -30 and +C., the molar ratio of said carbonyl compound to said hydroperoxide being between about 1:2 and 1:10.

4. The process of claim 3, wherein the said molar ratio is between about 1:25 and 1:5.

5. The process of claim 3, wherein said reaction temperature is between about -l() and 50C.

6. The process of claim 3, wherein said sulfonic acid catalyst is p-toluene sulfonic acid.

7. The process of claim 3 which is carried out in a solvent selected from the group consisting of linear aliphatic hydrocarbons having 6-10 carbon atoms, linear aliphatic halogenated hydrocarbons having 1 or 2 carbon atoms and from 1 to 4 chlorine atoms, aromatic hydrocarbons having from 6 to 9 carbon atoms which may be halogenated with l or 2 chlorine atoms, cycloaliphatic hydrocarbons having 6-10 carbon atoms and ethers.

Patent No.

I EGEO SACRINI and CLAUDIO CAVALLOTTI and that said Letters Patent are hereby corrected as shown below:

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 3,928,466 Dated December 23, 1975 It is certified that error appears in the above-identified patent Column 4, line 10: "partically" should read practical- 1y line 63: "product had product had" should read product had line 65: "98-99C" should read 58-59C Columns 5-6, Table l, lst formula:

ooc cn should CH=CH-CN read QCH:CH U

0OC(CH 1) OOC(CR;),

Columns 7-8, Table 2, 1st formula:

|| H I OOC(CH cH=CH-CH Should LH=CH CH OOC(CH.1)=

ocucun, read Column 9, line 26: "alkyl cyc-loalkyl" should read alkyl and cycloalkyl I Column 10, line 17: "and phenylalkyl" should read and halogen substituted phenylalkyl Signed and Sealed this Serenteenth Day Of August 1976 [SEAL] Arrest:

om s'uALL DANN I Commissioner ofPdrems and Trademarks RUTH C. MASON A ltesring Of fiber 

1. AN ORGANIC PERIOXIDE HAVING THE FORMULA:
 2. The peroxide of claim 1 which is selected from the group consisting of 1-phenyl-3,3-di(ter.-butyl-peroxy)-propene-1; 1-phenyl-3,3-di(cumyl-peroxy)-propene-1; 1-phenyl-3,3-di(ter.-butyl-peroxy)-butene-1; 1-phenyl-3,3-di(cumyl-peroxy)-butene-1; 1-phenyl-3-ter.-butyl-peroxy-3-cumyl-peroxy-butene-1; 1-cyclohexylidene-2,2-di(ter.-butyl-peroxy)-ethane; 1,1-di(ter.-butyl-peroxy)-2-benzylidene-cyclohexane; 1,1-di(ter.-butyl-peroxy)-2,6-di(4-hydroxy-benzylidene)cyclohexane; 1,1-di(ter.-butyl-peroxy)-2,6-di(4-isopropyl-benzylidene)cyclohexane; 1-cyclohexyl-3,3-di(ter.-butyl-peroxy)-butene-1; 2,3-di(phenyl)-4-di(ter.-butyl-peroxy)-butene-2; 1-phenyl-3,3-di(cyclohexen-2-yl-1-peroxy)propene-1; 1-phenyl-3,3-di(cyclohexen-2-yl-1-ethyl-1-peroxy)propene-1; 1-phenyl-3,3-di(tetralin-1-peroxy)propene-1 and 1-phenyl-3,3-di(tetralin-1-methyl-1-peroxy)propene-1.
 3. A process for the preparation of an organic peroxide having the formula:
 4. The process of claim 3, wherein the said molar ratio is between about 1:2.5 and 1:5.
 5. The process of claim 3, wherein said reaction temperature is between about -10* and 50*C.
 6. The process of claim 3, wherein said sulfonic acid catalyst is p-toluene sulfonic acid.
 7. The process of claim 3 which is carried out in a solvent selected from the group consisting of linear aliphatic hydrocarbons having 6-10 carbon atoms, linear aliphatic halogenated hydrocarbons having 1 or 2 carbon atoms and from 1 to 4 chlorine atoms, aromatic hydrocarbons having from 6 to 9 carbon atoms which may be halogenated with 1 or 2 chlorine atoms, cycloaliphatic hydrocarbons having 6-10 carbon atoms and ethers. 